Atomically Precise Iron Catalysis for Efficient Electrochemical Cycloaddition of CO ₂ With Low‐Cost Feedstocks to Styrene Carbonate

Electrocatalytic CO 2 cycloaddition provides a green route for the synthesis of cyclic carbonates under mild conditions. However, activating sterically hindered styrene oxide (SO) remains challenging due to its weak electron‐withdrawing phenyl group. Herein, we report an atomically dispersed Fe/N‐C single‐atom catalyst (Fe 1.98 ─N─C) for the efficient conversion of SO and CO 2 to styrene carbonate (SC). The catalysts deliver a 78% yield and 99% selectivity within 6 h, outperforming most reported electrocatalytic systems. Fe 1.98 ─N─C exhibits higher activity than an Fe nanoparticle catalyst and Fe‐free ZIF‐NC. Aberration‐corrected STEM and XAFS confirm the atomic dispersion of Fe and the formation of Fe─N 4 coordination sites. In situ FTIR, EPR, and DFT calculations reveal that Fe─N 4 sites promote SO ring‐opening and CO 2 activation through a synergistic Lewis acid‐base mechanism. Controlled Fe incorporation enhances the surface area and porosity, facilitating the cycloaddition process. This work provides a robust strategy for designing MOF‐derived single‐atom catalysts for sustainable electrochemical CO 2 utilization.